Iodine-surface active carrier germicidal preparations



United States Patent IODlNE-SURFACE ACTIVE CARRIER GERMICIDAL PREPARATIONS Albert Katz, Hollis Hills, N. Y., and Morris v. Shelanski, Atlantic City, N. J., assignors to West Laboratories, Ilo, Long Island City, N. Y., a corporation of New ork No Drawing. Application November 19, 1956 Serial No. 622,784

11 Claims. (Cl. 167-93) This invention relates to germicidal compositions wherein elemental iodine is complexed with and stabilized and solubilized by certain surface active substances. More particularly the invention relates to germicidal compositions of the class described wherein iodine is complexed with or carried by an ethylene oxide condensate of stearic acid or castor oil providing preparations readily soluble in water in forming solutions from which iodine is gradually released to exert its germicidal action. The application is a continuation-in-part of our pending applications Serial Nos. 229,253 and 229,254, both filed on May 31, 1951, now abandoned.

The broad germicidal, fungicidal and virucidal activity of free iodine has long been recognized, but the utilization of such activity has been hindered by the very low solubility of iodine in water and its relative instability in aqueous solution. Preparations such as tincture of iodine and Lugols solution in which iodine is solubilized in water to a limited extent by means of sodium or potassium iodide have certain effectiveness,-but are objectionable due to their irritating nature and to the characteristic staining caused by such preparations.

The new germicidal compositions in accordance with the present invention are non-irritating, non-staining and can be compounded in a way to solubilize iodine to an extent far beyond that possible with solutions such as tincture of iodine or Lugols solution. In these new compositions iodine is complexed with certain surface active agents which are ethylene oxide condensates of castor oil or C to C alkyl fatty acid, and might more properly be referred to as polyoxyethylene condensates since they contain from about 8' to 60 mols of ethylene oxide per mol of castor oil or alkyl fatty acid. Such condensates are commercially available from a number of sources and the selection of the particular type of condensate, i. e. whether higher or lower methylene oxide content will depend in part upon the particular physical chemical properties desired in the germicidal composition. A suitable general purpose condensate of the castor oil type is one containing about 15 to 40 mols of ethylene oxide per mol of castor oil. In the case of ethylene oxide-alkyl fatty acid condensates, those most generally suitable contain from 15 to 35 mols of ethylene oxide per mol of alkyl fatty acid.

Ethylene oxide condensates of castor oil or alkyl fatty acids such as stearic acid are themselves materials of very low toxicity.

When the ethylene oxide condensates of castor oil or alkyl fatty acid are complexed with elemental iodine, the iodine apparently dissolves in and becomes loosely bound to the ethylene oxide condensates. A small portion of the iodine may chemically react and become chemically bound, but the bulk of the iodine is gradually releasable in aqueous media to behave and function as elemental iodine in the exertion of its germicidal, fungicidal, or virucidal activity. It is'to be noted, however, that the complexing or binding of the iodine persists in aqueous solution, with theiodine being released only as 2,840,510 Patented June 24, 1958 cally mixing together the ethylene oxide condensate of castor oil or alkyl fatty acid with elemental iodine at room temperature, or at moderately elevated temperalures until solution of the iodine in the ethylene oxide condensate is completed. Alternatively, either or both components can be dissolved in a suitable solvent, such as ethanol, isopropanol, or the like, or the ethylene oxide condensate can first be dissolved in water and the elemental iodine, or iodine in solvent solution then mixed with the condensate to efiect complexing. When solvents are thus employed, they may or may not be removed depending on the intended use of the complex, since the particular manner of complexing, whether by direct dissolving or by the use of solvents does not seem to effect the nature or properties of the resulting complex,

The amount of iodine complexed with the ethylene oxide condensate of castor oil or alkyl fatty acid can suitably be about 0.5% to 15% based on the weight of the condensate. Realizing that elemental iodine has efiective germicidal, fungicidal and virucidal properties in aqueous media at dilutions as lowas about 5 p. p. m., it will be evident that compositions containing 0.5 of iodine based upon weight of complex can be diluted about 1000 times with water and still provide a germicidal active solution,,whereas the compositions containing 2% of iodine can be diluted with about 4000 volumes of water and still provide a germicidally active solution.

The new complexes of iodine with ethylene oxide condensates of alkyl fatty acid or castor oil can be utilized in many types of disinfectant and germicidal preparations for environmental sanitation and the like, but are particularly adapted by reason of their low toxicity for use in oral hygiene, or the like. The compositions may be incorporated for example, in a liquid concentrate adapted for further dilution by the user and ultimate use as a mouth Wash or gargle. Alternatively, the compositions may be incorporated in a dentifrice of either the liquid, paste or powder type, or in an oral lozenge. In any of these uses the new compositions willefifectively reduce the bacterial flora in the mouth and the associated odors.

In these various uses and applications of the new compositions for oral hygiene, the basic aim is to provide iodine concentrations of preferably to 1000 p. p. m. in the mouth during the period of use of the preparation. To this end, preparations such as dentifrices and oral lozenges should contain about 0.5% to 10%- and preferably about 0.5 to 5% of the iodine complex based on the total weight of the preparation. A mouth wash concentrate may contain about1% to 10% and'suitably about 1% to 5% of iodine complex provided the intended dilution of such concentrate for use as a mouth wash or gargle is about 1 to 20. If intended dilutions of a mouth wash or gargle were to be distinctly different from the 1 to 20 proportion above mentioned, the concentration of iodine complex in the mouth wash concentrate should be proportionately modified.

I The following examples show how the new complexes of iodine with ethylene oxide condensates of castor oil or alkyl fatty acid can be prepared, as well as how typical preparations including such complexes may be formulated. It is to be understood, however, that these examples are given by way of illustration and not of limitation. 1

3 Example I An ethylene oxide castor oil condensate (99 parts by weight) containing about 39 mols of ethylene oxide per mol of castor oil is mixed with l part by weight of elemental iodine (crystals) by melting the condensate and stirring in the iodine and then cooling, thereby forming a' solution or complexof iodine with the ethylene oxide castoroil condensate.

When the foregoing procedure is modified by" making a concentrated solution of iodine in ethanol, thoroughly mixing the ethanol-iodine solution with the ethylene oxide-castor oil condensate, and then evaporating at room temperature to remove the ethanol, the product obtained is an iodine complex which is identical in 'propertieg with the product obtained by mechanical mixing of the components.

Example II An ethylene oxide-stearic acid condensate (90 parts by weight) containing about 16 mols of ethylene oxide per mol of stearic acid is mixed with parts by weight of iodine crystals by melting the condensate and stirring in the iodine and then cooling, thereby forming'a solution or complex of iodine with the ethylene oxide-stearic acid condensate. t

When the foregoing procedure is modified by thoroughly mixing a concentrated alcohol-iodine solution with the ethylene oxide-stearic acid condensate, and then evaporating at room temperature to remove the alcohol, the iodine complex so obtained is identical in properties with the product obtained by mechanical mixing of the components.

Example III Example IV An ethylene oxide lauric acid condensate (90 parts by weight) containingabout 10 mols. of ethylene oxide per mol of lauric acid is mixed with 10 parts of iodine crystals by melting the condensate and stirring in the iodine and then jcooling, thereby forminga solution or complex of iodinein the ethylene oxide lauric acid condensate.

When the foregoing procedure is modified by thoroughly mixing the concentrated ethanol-iodine solution with the ethylene oxide lauric acid condensate, andthen evaporating atroom temperature to remove the ethanol, the product obtained is an iodine complex which is identical in properties with the product obtained by mechanical mixing of the components. c r

In the foregoing examples the amountof iodine can be variedin proportion to the ethyleneoxide condensate from about 0.5 to of the weight of the condensate. When a solvent such as ethanol, isopropanol or the like is employed the amount can vary from a minimum amount required to dissolve the iodine to some higher amount practical to fluidize the mixture and thus facili- -tate complexing of iodine with the ethylene oxide condensate. 4

Example V t Example I (containing 10% iodine) and having the following formulation expressedin parts by" weight:

Gm. Iodine complex 1 Talc 50 Sodium lauryl sulfate 8 Glycerin 35 Citric acid Example VI A typical powdered dentrifrice is prepared using a complex of iodine and ethylene oxide-stearic acid condensate as prepared in Example Ill (containing 10% iodine) and having the following formulation expressed in parts by weight:

Gm. Iodine complex 1 Talc 93.5 Sodium lauryl sulfate 5.3 Soluble saccharine 100 Citric acid 30 Menthol 20 Anethole 20 The iodine complex is suitably first mixed with the tale and the other components then added with constant agitation of the mixture. The order of adding components is not important, but mixing should be continued until a uniform powder is obtained.

7 Example VII Typical oral lozenges are prepared using an iodine complex with ethylene stearic acid condensate as prepared in Example II, but containing 2% iodine, and having the following formulation expressed in parts by weight:

Parts Iodine complex 15 Granulated sugar 100 Water 34 Tartaric acid 0.5 Flavoring material (methanol salicylate) 0.3

The components with the exception of the iodine complex and flavoring are boiled, and then cooled. While still liquid, but below boiling temperature the iodine complex and flavoring agent are added and thoroughly mixed with the warm liquid. As cooling continues and themass becomes plastic, it is pulled into rods and cut to convenient sized drops or pieces. Alternatively, the plastic material can be molded or die-formed into pieces of desired shape and characterization.

Example VIII A month washis prepared using a complex of iodine with stearic acid ethylene oxide condensate containing 27 mols of ethylene oxide per mol of stearic acid and a quantity of iodine to provide 11.7% titratable iodine (when the complex is titrated with 0.01 N sodium thiosulfate) and having the following formulation expressed in parts by Weight:

Parts Iodine complex 8 Boric acid 1.6

Menthol 0.6 Anethole e 0.3

Ethanol I Q. 13 Water, q.-s. 100 parts by weight This month wash is diluted prior to use with 5 to 40 and preferably about 20 volumes of water for each volume of mouth wash concentrate employed.

Example IX A mouth wash is prepared using a complex of iodine and ethylene castor oil condensate containing 39 mols of ethylene oxide per mol of castor oil and said complex having 6.25% of iodine (as indicated by titration with 0.01 N sodium thiosulfate) and having the following formulation expressed in parts by weight:

Water, q. s. 100 parts In use the mouth wash of the above formulation is diluted at the rate of 1 part of mouth wash concentrate to each 5 to 40 parts of water and preferably at the rate of 1 part to 20 parts of water.

Various changes and modifications in the new compositions herein disclosed will occur to those skilled in the art and to the extent that such changes and modifications are embraced by the appended claims, it is to be understood that they constitute part of our invention.

We claim: a

1. A germicidal composition comprising a complex of iodine with a surface active carrier selected from the group consisting of condensates of ethylene oxide with castor oil containing 8 to 60 mols of ethylene oxide per mol of castor oil, and condensates of ethylene oxide with a C to C alkyl fatty acid containing 8 to 60 mols of ethylene oxide per mol of alkyl fatty acid, andsaid complex containing about 0.5% to of iodine based on the weight of said carrier.

2. A germicidal composition comprising a complex of iodine with a surface active carrier which is a condensate of ethylene oxide with castor oil containing 8 to 60 mols of ethylene oxide per mol of castor oil, and said complex containing about 0.5% to 15% of iodine based on the weight of said carrier.

3. A germicidal composition comprising a complex of iodine with a surface active carrier which is a condensate of ethylene oxide with castor oil containing 15 to 40 mols of ethylene oxide per mol of castor oil, and said complex containing about 0.5% to 15% of iodine based on the weight of said carrier.

4. A germicidal composition comprising a complex of iodine with a surface active carrier which is a condensate of ethylene oxide and a C to C alkyl fatty acid containing 8 to mols of ethylene oxide per mol of alkyl fatty acid, and said complex containing about 0.5 to 15 of iodine based upon the weight of said carrier.

5. A germicidal composition as defined in claim 4 wherein the surface active carrier is an ethylene oxide stearic acid condensate.

6. A germicidal composition as defined in claim 4 wherein the surface active carrier is an ethylene oxide lauric acid condensate.

9. A germicidal preparation for oral hygiene as defined in claim 8 wherein said germicidal component is incorporated in a dentifrice.

10. A germicidal preparation for oral hygiene as defined in claim 8 wherein said germicidal component-is incorporated in a lozenge.

11. A germicidal preparation for oral hygiene as defined in claim 8 wherein said germicidal component is incorporated in a mouth wash.

References Cited in the file of this patent Chemical and Engineering News, Feb. 19, 1951, p. 664. 

1. A GERMICIDAL COMPOSITION COMPRISING A COMPLEX OF IODINE WITH A SURFACE ACTIVE CARRIER SELECTED FROM THE GROUP CONSISTING OF CONDENSATES OF ETHYLENE OXIDE WITH CASTOR OIL CONTAINING 8 TO 60 MOLS OF ETHYLENE OXIDE PER MOL OF CASTOR OIL, AND CONDENSATES OF ETHYLENE OXIDE WITH A C12 TO C18 ALYL FATTY ACID CONTAINING 8 TO 60 MOLS OF ETHYLENE OXIDE PER MOL OF ALYL FATTY ACID, AND SAID COMPLEX CONTAINING ABOUT 0.5% TO 15% OF IODINE BASED ON THE WEIGHT OF SAID CARRIER. 